Effects of Iron and Graphene Oxide on the Photocatalytic activity of Titanium Dioxide for Methylene Blue Degradation

Document Type : Research Paper


1 MSc Student, Faculty of Chemical Engineering, Urmia University of Technology, Urmia, Iran

2 Assoc. Prof., Faculty of Chemical Engineering, Urmia University of Technology, Urmia, Iran


Among the photocatalysts, Titanium dioxide (TiO2) is mostly used for wastewater treatment. Nevertheless, large band gap, rapid recombination of electron–hole along with difficult separation process limits TiO2 applications in industrial scale. In this study, the photocatalytic activity and separation of TiO2 were improved by combined application of Fe3O4 and graphene oxide. X-ray powder diffraction (XRD), scanning electron microscopy (FESEM), and magnetization measurement (VSM) was utilized to characterize the sample and the photocatalytic degradation of methylene blue under visible light irradiation was evaluated by UV-vis spectrophotometer. The results indicate the successful preparation of purified TiO2/Fe3O4/GO nanocomposite by a two-step sol gel-hydrothermal method. The enhanced photocatalytic activity of nanocomposite is attributed to the simultaneous application of iron oxide and graphene oxide. The maximum photocatalytic decoloration (90%) is achieved within 80 min under lamp irradiation. The superparamagnetism of nanocomposites provided a convenient route for separation of the catalyst from the reaction mixture by an external magnet.


Ahmad, A., Mohd-Setapar, S. H., Chuong, C. S., Khatoon, A., Wani, W. A., Kumar, R., et al. 2015. Recent advances in new generation dye removal technologies: novel search for approaches to reprocess wastewater. RSC Advances, 5, 30801-30818.
Al-Ghouti, M., Khraisheh, M., Allen, S. & Ahmad, M. 2003. The removal of dyes from textile wastewater: a study of the physical characteristics and adsorption mechanisms of diatomaceous earth. Journal of Environmental Management, 69, 229-238.
Beydoun, D., Amal, R., Low, G. & Mcevoy, S. 2002. Occurrence and prevention of photodissolution at the phase junction of magnetite and titanium dioxide. Journal of Molecular Catalysis A: Chemical, 180,
Carneiro, P. A., Osugi, M. E., Sene, J. J., Anderson, M. A. & Zanoni, M. V. B. 2004. Evaluation of color removal and degradation of a reactive textile azo dye on nanoporous TiO2 thin-film electrodes. Electrochimica Acta, 49, 3807-3820.
Chakrabarti, S. & Dutta, B. K. 2004. Photocatalytic degradation of model textile dyes in wastewater using ZnO as semiconductor catalyst. Journal of Hazardous Materials, 112, 269-278.
Chang, Y.-N., Ou, X.-M., Zeng, G.-M., Gong, J.-L., Deng, C.-H., Jiang, Y., et al. 2015. Synthesis of magnetic graphene oxide–TiO2 and their antibacterial properties under solar irradiation. Applied Surface Science, 343, 1-10.
Cong, Y., Long, M., Cui, Z., Li, X., Dong, Z., Yuan, G., et al. 2013. Anchoring a uniform TiO2 layer on graphene oxide sheets as an efficient visible light photocatalyst. Applied Surface Science, 282, 400-407.
Gad-Allah, T. A., Kato, S., Satokawa, S. & Kojima, T. 2009. Treatment of synthetic dyes wastewater utilizing a magnetically separable photocatalyst (TiO2/SiO2/Fe3O4): parametric and kinetic studies. Desalination, 244,
Harifi, T &. Montazer, M. 2014. A novel magnetic reusable nanocomposite with enhanced photocatalytic activities for dye degradation. Separation and Purification Technology, 134, 210-219.
Houas, A., Lachheb, H., Ksibi, M., Elaloui, E., Guillard, C. & Herrmann, J.-M. 2001. Photocatalytic degradation pathway of methylene blue in water. Applied Catalysis B: Environmental, 31, 145-157.
Jing, J., Li, J., Feng, J., Li, W. & William, W. Y. 2013. Photodegradation of quinoline in water over magnetically separable Fe3O4/TiO2 composite photocatalysts. Chemical Engineering Journal, 219, 355-360.
Kang, S.-F., Liao, C.-H. & Po, S.-T. 2000. Decolorization of textile wastewater by photo-Fenton oxidation technology. Chemosphere, 41, 1287-1294.
Li, L., Li, X., Duan, H., Wang, X. & Luo, C. 2014. Removal of Congo Red by magnetic mesoporous titanium dioxide–graphene oxide core–shell microspheres for water purification. Dalton Transactions, 43, 8431-8438.
Li, Z.-J., Huang, Z.-W., Guo, W.-L., Wang, L., Zheng, L.-R., Chai, Z.-F., et al. 2017. Enhanced photocatalytic removal of uranium (VI) from aqueous solution by magnetic TiO2/Fe3O4 and its graphene composite. Environmental Science and Technology, 51, 5666-5674.
Li, Z.-Q., Wang, H.-L., Zi, L.-Y., Zhang, J.-J. & Zhang, Y.-S. 2015. Preparation and photocatalytic performance of magnetic TiO2–Fe3O4/graphene (RGO) composites under VIS-light irradiation. Ceramics International,
41, 10634-10643.
Liang, Y., He, X., Chen, L. & Zhang, Y. 2014. Preparation and characterization of TiO2–Graphene@ Fe3O4 magnetic composite and its application in the removal of trace amounts of microcystin-LR. RSC Advances, 4, 56883-56891.
Ma, J., Guo, S., Guo, X. & Ge, H. 2015. A mild synthetic route to Fe3O4@ TiO2-Au composites: preparation, characterization and photocatalytic activity. Applied Surface Science, 353, 1117-1125.
Maji, S. K., Mukherjee, N., Mondal, A. & Adhikary, B. 2012. Synthesis, characterization and photocatalytic activity of α-Fe2O3 nanoparticles. Polyhedron, 33, 145-149.
Mehrjouei, M., Müller, S. & Möller, D. 2015. A review on photocatalytic ozonation used for the treatment of water and wastewater. Chemical Engineering Journal, 263, 209-219.
Mishra, N. S., Reddy, R., Kuila, A., Rani, A., Mukherjee, P., Nawaz, A., et al. 2017. A review on advanced oxidation processes for effective water treatment. Current World Environment, 12, 470-490.
Nasr, M., Balme, S. B., Eid, C., Habchi, R., Miele, P. & Bechelany, M. 2016. Enhanced visible-light photocatalytic performance of electrospun rGO/TiO2 composite nanofibers. The Journal of Physical Chemistry C, 121, 261-269.
Nazari, Y. & Salem, S. 2017. Magnetisation of TiO2/reduced graphene oxide nano photocatalyst. International Proceedings of Chemical, Biological and Environmental Engineering, 102, 50-56.
Niu, H., Wang, Q., Liang, H., Chen, M., Mao, C., Song, J., et al. 2014. Visible-light active and magnetically recyclable nanocomposites for the degradation of organic dye. Materials, 7, 4034-4044.
Özkan, A., Özkan, M., Gürkan, R., Akcay, M. & Sökmen, M. 2004. Photocatalytic degradation of a textile azo dye, Sirius Gelb GC on TiO2 or Ag-TiO2 particles in the absence and presence of UV irradiation: the effects of some inorganic anions on the photocatalysis. Journal of Photochemistry and Photobiology A: Chemistry, 163, 29-35.
Peng, G., Ellis, J. E., Xu, G., Xu, X. & Star, A. 2016. In situ grown TiO2 nanospindles facilitate the formation of holey reduced graphene oxide by photodegradation. ACS Applied Materials and Interfaces, 8, 7403-7410.
Qadri, S., Ganoe, A. & Haik, Y. 2009. Removal and recovery of acridine orange from solutions by use of magnetic nanoparticles. Journal of Hazardous Materials, 169, 318-323.
Ren, W., Ai, Z., Jia, F., Zhang, L., Fan, X. & Zou, Z. 2007. Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline TiO2. Applied Catalysis B: Environmental, 69, 138-144.
Rezaei, M. & Salem, S. 2016a. Optimal TiO2–graphene oxide nanocomposite for photocatalytic activity under sunlight condition: synthesis, characterization, and kinetics. International Journal of Chemical Kinetics, 48, 573-583.
Rezaei, M. & Salem, S. 2016b. Photocatalytic activity enhancement of anatase–graphene nanocomposite for methylene removal: degradation and kinetics. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 167, 41-49.
Rezaei, M., Salem, S. & Salem, A. 2016c. Enhancement of photocatalytic activity of TIO2 under visible light irradiation by graphene oxide nano sheets. Journal of Color Science and Technology, 10(1), 13-21. (In Persian)
Stengl, V., Popelková, D. & Vlácil, P. 2011. TiO2 graphene nanocomposite as high performace photocatalysts. The Journal of Physical Chemistry C, 115, 25209-25218.
Subramani, A. & Jacangelo, J. G. 2015. Emerging desalination technologies for water treatment: a critical review. Water Research, 75, 164-187.
Tang, Y., Zhang, G., Liu, C., Luo, S., Xu, X., Chen, L., et al. 2013. Magnetic TiO2-graphene composite as a high-performance and recyclable platform for efficient photocatalytic removal of herbicides from water. Journal of Hazardous Materials, 252, 115-122.
Toor, A. P., Verma, A., Jotshi, C., Bajpai, P. & Singh, V. 2006. Photocatalytic degradation of Direct Yellow 12 dye using UV/TiO2 in a shallow pond slurry reactor. Dyes and Pigments, 68, 53-60.
Wang, W., Yu, J., Xiang, Q. & Cheng, B. 2012. Enhanced photocatalytic activity of hierarchical macro/mesoporous TiO2–graphene composites for photodegradation of acetone in air. Applied Catalysis B: Environmental, 119, 109-116.
Wu, W., Xiao, X., Zhang, S., Ren, F. & Jiang, C. 2011. Facile method to synthesize magnetic iron oxides/TiO2 hybrid nanoparticles and their photodegradation application of methylene blue. Nanoscale Research Letters, 6, 533.
Xiao, J., Xie, Y. & Cao, H. 2015. Organic pollutants removal in wastewater by heterogeneous photocatalytic ozonation. Chemosphere, 121, 1-17.
Yao, Y., Li, G., Ciston, S., Lueptow, R. M. & Gray, K. A. 2008. Photoreactive TiO2/carbon nanotube composites: synthesis and reactivity. Environmental Science and Technology, 42, 4952-4957.
Yu, X., Liu, S. & Yu, J. 2011. Superparamagnetic γ-Fe2O3@ SiO2@ TiO2 composite microspheres with superior photocatalytic properties. Applied Catalysis B: Environmental, 104, 12-20.
Zhang, C., Chen, H., Ma, M. & Yang, Z. 2015. Facile synthesis of magnetically recoverable Fe3O4/Al2O3/molecularly imprinted TiO2 nanocomposites and its molecular recognitive photocatalytic degradation of target contaminant. Journal of Molecular Catalysis A: Chemical, 402, 10-16.
Zhang, G.-Y., Feng, Y., Xu, Y.-Y., Gao, D.-Z. & Sun, Y.-Q. 2012. Controlled synthesis of mesoporous α-Fe2O3 nanorods and visible light photocatalytic property. Materials Research Bulletin, 47, 625-630.
Zhang, H., Wu, X., Wang, Y., Chen, X., Li, Z., Yu, T., et al. 2007. Preparation of Fe2O3/SrTiO3 composite powders and their photocatalytic properties. Journal of Physics and Chemistry of Solids, 68, 280-283